Effects of ethoxylate structure on surfactant properties of ethoxylated fatty methyl esters

In the presence of a surface-modified Al-Mg composite oxide catalyst, ethoxylated fatty methyl esters with different hydrophobic group structures and different chain-lengths of polyoxyethylene were synthesized from fatty methyl esters by direct ethoxylation. Each ethoxylated fatty methyl ester obtained showed a narrow ethylene oxide (EO) adduct distribution. Foaming, ability to lower surface tension, ability to lower interfacial tension, wettability, and dye solubilization were measured. Ethoxylated methyl laurate with about 60 to 70% EO content was found to be the most suitable as a base surfactant for household detergents     

脂肪酸甲酯乙氧基化物的物化性能研究

对不同烷链和不同EO加合数的脂肪酸甲酯乙氧基化物的物化性能进行了测试,并对FMEE在洗衣粉中替代AEO9进行了初步研究。结果表明,与脂肪醇乙氧基化物相比,FMEE泡沫低,水溶速度快,对油脂增溶能力强,用棕榈油甲酯乙氧基化物替代AEO9在洗衣粉中应用可改善去污性能并降低成本。     

Methyl ester propoxylates

Insertion of propylene oxide into methyl esters is accomplished using a proprietary alkoxylation catalyst. The alkoxylation mechanism is believed to involve transesterification between the alkoxylated metal-alkoxide of the catalyst and the ester. Optimal alkoxylation conditions are discussed. The effect of inserting propylene oxide prior to ethoxylation on surface properties and foam performance is examined. Presented at the annual meeting of the American Oil Chemists' Society, Seattle, WA, May 1997.     

乙氧基化脂肪酸甲酯的性能及丙氧基化改性研究

以单碳酸或混合酸甲酯为原料，通过一步法乙氧基化反应合成了不同链长的脂肪酸和不同EO数的乙氧基化脂肪酸甲酯(EFME)，测定了EFME的物化性能和应用性能。结果表明，EFME具有低成本、低泡等特殊优点，性能依赖EO加成数变化连续可调整，EFME中的封端甲基是导致其性能不同于AEO的最重要的结构因素。用PO对EFME进行化学改性，先加成PO的产品的起泡力更低、流变性更好，与不改性产品相比起泡力降为原先的29％；稳泡性降为原先的22％；黏度降低为原先的44％。说明PO位于分子的亲水端侧较处于疏水端侧对产品的泡沫性和流变性的影响程度更大，通过PO改性可以进一步开发EFME的新用途。     

Influence of catalyst structure on direct ethoxylation of fatty methyl esters over Al-Mg composite oxide catalyst

During direct ethoxylation of fatty methyl ester over Al-Mg composite oxide catalyst, the activity was nearly proportional to the total number of active Al acidic sites on the catalyst surface per unit weight of catalyst. Lower active Al acidic site densities resulted in a narrower ethylene oxide (EO) adduct distribution of obtained ethoxylate. We developed a new catalyst with a large surface area on which many acidic sites are distributed uniformly by partially poisoning the Al acid sites of high-Al content Al-Mg composite oxide with alkali. This catalyst was used for direct ethoxylation of fatty methyl esters to obtain ethoxylated fatty methyl esters with narrow EO adduct distribution efficiently.     

Sea Buckthorn Oil Tocopherol Extraction's By‐Product Utilization in Green Synthesis of Polyurethane Coating

The focus of the present study is to utilize a by‐product obtained during extraction of tocopherols, a valuable vitamin E compound, from sea buckthorn (SBT) oil and in doing so find a reliable alternative to petrochemical based polyols. Bio‐based polyurethane (PU) is prepared by using SBT oil based fatty acid methyl ester polyesteramide polyols (SBTPEP) with toluene diisocyanate (TDI). The fatty acid methyl ester is converted to the corresponding fatty amide by reaction with diethanolamine. The formed fatty amide is then esterified with phthalic anhydride to synthesize polyesteramide polyol. Characterization techniques used to evaluate polyesteramide polyol are Fourier‐transform infrared spectroscopy (FTIR) and NMR. The cured PU coating is also put through various mechanical tests to analyze the physical properties. The cured PU coating shows good surface and mechanical properties. It shows a gloss value of 87.4 and passes impact, adhesion, and chemical resistance tests. It is hydrophobic which is evident from its contact angle of 100.2°. It has good thermal stability which is evident by its glass transition temperature of 53.9 °C. Use of phthalic anhydride contributes to the bio‐based characteristics of synthesized PU. Practical Application: The present study presents a synthesis route which has minimal dependence on hazardous feedstock by utilization of green feedstock. The results obtained from physical and mechanical evaluations favor the use of this PU formulation in the coating sector. The adhesion and impact strength test results show potential application in the industrial sector coatings where the applied coat must be able to withstand high levels of physical stress and strain. The presence of aromatic rings and oil‐based moiety, that is the fatty acid hydrocarbon chain, contributes to the hydrophobic nature of the PU coating. Hydrophobic coatings have tremendous application in various fields such as marine coatings, automotive, electronics, and decorative coatings. These are potential fields of application for the synthesized green PU coating obtained from tocopherol extraction by‐products.     

Interfacial Tensions of Ethoxylated Fatty Acid Methyl Ester Solutions Against Crude Oil

The dynamic interfacial tension (IFT) of ethoxylated fatty acid methyl ester solutions against n‐alkanes, kerosene, and diluted heavy oil have been investigated by spinning drop interfacial tensiometry. The influences of ethylene oxide (EO) groups and alkyl chain length on IFT were investigated. The experiment results show that the water solubility decreases with an increase in alkyl chain length or a decrease in EO groups. The ability to lower the interfacial tension against hydrocarbons improves with both increasing alkyl chain length and EO group at the best hydrophilic‐lipophilic balance, which can be attributed to the enhancement of the interfacial hydrophobic interactions and the rearrangement of interfacial surfactant molecules. The mixed adsorption of surfactant molecules and surface‐active components may reduce IFT to a lower value. C₁₈=E₃ shows the best synergism with surface‐active components. However, the IFT values against pure crude oil are obviously higher than those against hydrocarbons, which may be caused by the nature of heavy oil.     

磺化合成鲸蜡油/硫酸酯类表面活性剂复合体系的性能研究

以降膜式SO3磺化合成鲸蜡油(SSW)为对象,考察了磷酸酯类表面活性剂(PES)对SSW形成复合体系的影响。通过比较拟三元相图中油相区域比例,确定3种SSW/PES复合体系中PES的最优用量:w(A8EO5PNa)=1.5%,w(A9EO5PNa)=1.0%,w(A12EO3PNa)=0.5%。根据最优配方研究了复合体系的表面张力、革表面动态润湿角、乳液稳定性、临界胶束浓度(cmc)及粒度分布。结果表明:SSW/A9EO5PNa复合体系表面张力为27.39 mN/m,润湿渗透能力强,临界胶束浓度低,乳液稳定性好,乳液平均粒径为78.7 nm,更适合应用于皮革加脂剂。     

脂肪酸甲酯磺酸盐的研究及应用进展

论述了脂肪酸甲酯磺酸盐的发展状况。介绍了脂肪酸甲酯磺酸盐优良的洗涤性能、可生物降解性和绿色环保等优异性能。对国内外脂肪酸甲酯磺酸盐的发展及生产技术进行了回顾。对我国脂肪酸甲酯磺酸盐的发展状况、未来趋势及发展前景进行了展望。面对石油资源日趋紧张,必然将人们引向油脂化工这一传统领域。脂肪酸甲酯磺酸盐丰富的原料来源、成本优势以及使用优势,使这些油脂基表面活性剂更具市场竞争力。     

聚酯醚型消泡剂的一步法合成及消泡性能研究

以月桂酸甲酯、环氧乙烷(EO)、环氧丙烷(PO)为原料,MCT-09为催化剂,一步法合成了脂肪酸甲酯无规聚醚(FMERP)聚酯醚型消泡剂.反应条件优化为:反应温度195～200 ℃,压强0.3～0.4 MPa,搅拌速率600 r/min,催化剂用量6.05 g Cat./mol脂肪酸甲酯.通过红外光谱(IR)、核磁共振谱图(1HNMR、13CNMR)对产品进行了表征,结果表明所合成的产品为目标产物.产品与市场聚醚消泡剂L-61进行了比较,表明FMERP的消泡和抑泡性能比L-61好,消泡效率和抑泡效率最高分别达到72.2%和61.1%.     

BADCy/MMA半互穿网络的制备及性能表征

在加热熔融的氰酸酯树脂(BADCy)中加入甲基丙烯酸甲酯(MMA)单体(同步合成法)或MMA预聚体(异步合成法)并引发使其发生本体聚合,制备了具有半互穿聚合物网络结构的氰酸酯树脂/聚甲基丙烯酸甲酯(BADCy/MMA-SIPN),通过力学性能测试,红外及DSC分析研究了MMA含量对体系力学性能和热性能的影响。结果表明,互穿网絡的形成使氰酸酯树脂体系的力学性能和耐热性能都有较大的提高,冲击强度、弯曲强度及玻璃化温度分别提高了97.8%、58.6%和65℃。     

棉油酸甲酯改性胺固化剂的合成及性能研究

利用棉油酸甲酯制备了一种环氧树脂固化剂棉油酸甲酯改性胺,研究了棉油酸甲酯改性胺用量对环氧树脂体系的力学性能和热性能的影响,利用红外光谱、热分析、动态力学分析讨论了棉油酸甲酯改性胺的结构、环氧树脂固化物的性能。结果表明,环氧树脂固化物的拉伸性能、弯曲性能和冲击强度随着棉油酸甲酯改性胺用量的增加而增加。     

脂肪酸甲酯乙氧基化物的生产与应用

介绍了低泡沫非离子表面活性剂脂肪酸甲酯乙氧基化物（FMEE）的性质，如耐硬水、净洗性能、低温流动性、生态环保等，叙述了FMEE的合成机理及生产方法，以及其在造纸、煤碳浮选、硬表面清洗、纺织印染等领域相关应用。认为应加强合成FMEE催化剂的改进，提高其性能和效率；合成出不同结构的FMEE，并实现与其他表面活性剂复配。     

Methyl ester ethoxylates

Conventional ethoxylation of fatty methyl esters, or other fatty-fatty esters or diesters, produces poor yields of the desired ethoxylated ester. A proprietary ethoxylation catalyst, currently in use to produce “peaked” or “narrow-range” alcohol ethoxylates, has been found to successfully insert ethylene oxide into the ester linkage of fatty esters. The mechanism for this insertion likely involves an ethoxylation-transesterification step in the ethoxylation process. Physical, performance, and environmental/human safety properties were evaluated. Results, in general, show that methyl ester ethoxylates behave similarly to alcohol ethoxylates with the exception of having a lower foam profile and being less irritating. Presented at the Annual Meeting of the American Oil Chemists’ Society, Indianapolis, Indiana.     

Synergism and Performance Optimization in Liquid Detergents Containing Binary Mixtures of Anionic–Nonionic, and Anionic–Cationic Surfactants

In this paper evaluation of surface active and application properties in liquid detergent formulations containing binary mixtures of anionic–nonionic, and anionic–cationic surfactants is discussed. Surfactants used include: linear alkylbenzene sulfonate (LAS), alcohol ether sulfate (AES-2EO), alcohol ethoxylate (AE-7EO), lauryl dimethyl amine oxide, and alkyl hydroxyethyl dimethyl ammonium chloride (AHDAC). Surface active parameters relating to the effectiveness and efficiency of surface tension reduction were determined from the surface tension data. Non-ideal solution theory was used to determine the degree of interactions between the two surfactants, and the conditions under which a mixture of two surfactants show synergism in surface active properties. Our data indicated that synergism in mixed surfactants increases with the degree of charge difference between the surfactants. In both mixed micelle and mixed monolayer formation, the degree of interactions between the two surfactants in the mixture increased in the following order: LAS/AE < AES-2EO/amine oxide < AES-2EO/AHDAC. This synergistic behavior as presented in this paper leads to unique application properties and improved performance in terms of foam volume, and soil removal which has applications in formulation of dishwashing liquids, and laundry detergents.     

超支化聚磷酸酯改性PP的研究

以新型的超支化聚磷酸酯(HPPE)对聚丙烯(PP)进行共混改性,研究了HPPE的用量和分子量对PP/HPPE复合材料性能的影响,还通过扫描电子显微镜(SEM)观察其试样冲击断面的微观形态并研究其增韧机理.结果表明,HPPE对PP/HPPE复合材料的冲击强度影响明显,当HPPE-1用量为3份时冲击强度可提高143.56%;熔体流动速率也有提高,但拉伸强度、弯曲强度和维卡软化点温度有微小下降,其增韧机理为两相"海-岛"结构增韧.     

Structural Analyses of Hydrated Crystals in Mixed Green Surfactant Systems: α‐Sulfonated Fatty Acid Methyl Ester Salt and Fatty Acid Soap Mixtures

α‐Sulfonated fatty acid methyl ester salts (MES), synthesized from renewable plant resources, are an example of green surfactants used in eco‐friendly washing detergents because of their excellent detergent properties, biodegradability, and enzyme stability. Although various physicochemical properties of MES crystals and micelles have been studied, mixed systems composed of MES and other surfactants have not been well studied. We investigated the crystalline structures of hydrated solids in mixed systems containing MES and soaps, which have been utilized as detergents, using small‐ and wide‐angle X‐ray scattering (SWAXS), differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR) spectroscopy techniques. The minimum dissolution temperature, determined by visual observation, of a 4:1 M ratio of the sodium salt of α‐sulfonated palmitic acid methyl ester (C₁₆MES‐Na) and sodium palmitate (C₁₆‐Na), is indicative of a eutectic mixture. SWAXS measurements reveal that C₁₆MES‐Na and C₁₆‐Na crystals are formed separately in this system. Eutectic mixtures were also observed for the C₁₆MES‐Na/C₁₆MES‐K (α‐sulfonated palmitic acid methyl ester potassium salt) system and in the C₁₆MES‐K/C₁₆‐Na system. Furthermore, in addition to C₁₆MES‐K and C₁₆‐Na crystals, C₁₆MES‐Na crystals were also formed in the C₁₆MES‐K/C₁₆‐Na system, through counterion exchange during crystallization.     

Properties of Ethoxylated Castor Oil Acid Methyl Esters Prepared by Ethoxylation over an Alkaline Catalyst

The synthesis and properties of ethoxylated castor oil acid methyl esters (ECAME) were investigated. Ethylene oxide (EO) can react directly with the ester group and hydroxyl group of castor oil acid methyl esters in the presence of an alkaline catalyst. ECAME with different average EO adduct numbers were synthesized and, through testing the degree of EO addition, it was found that only a few EO moieties (2–4) inserted into the hydroxyl group. In addition, the physicochemical properties of ECAME were studied. ECAME can be used as nonionic surfactants with good properties.     

Rapid Screening of an Acid‐Catalyzed Triglyceride Transesterification in a Mesoscale Reactor

A mesoscale oscillatory baffled reactor (meso‐OBR) served as a continuous screening platform to rapidly investigate the operating conditions for acid‐catalyzed production of fatty acid methyl ester (FAME) from triglyceride feedstock. The acid catalyst was 4‐dodecylbenzenesulfonic acid (DBSA) and the triglyceride feedstock was rapeseed oil (RSO). The parameter space was explored by means of a design of experiments (DoE) methodology. The variables screened were methanol‐to‐RSO molar ratio, catalyst‐to‐oil molar ratio, and residence time. Over 98 % conversion of RSO to FAME could be achieved under optimized conditions.     

Effect of alkyl carbon chain length and ethylene oxide content on the performance of linear alcohol ethoxylates

A grid of 30 surfactants varying from C₈ to C₁₈ in carbon chain length and from 40 to 80% in ethylene oxide (EO) content were examined to determine the effect of molecular structure on the physical properties (density, melting point, solution viscosity) and performance properties (surface activity, detergency, hard-surface cleaning, foaming, wetting) of linear alcohol ethoxylates. Results show that while physical propeties are influenced primarily by EO content, both carbon chain length and EO content are important to performance. Optimum carbon chain length is also shown to depend strongly on surfactant concentration. Presented at the AOCS meeting in New Orleans in May 1987.